Insecticidal compositions and methods of killing insects using a mixture of cytrolane and chlorphenamidine

ABSTRACT

A composition for controlling certain lepidepteran larvae, in particular those which harm to cotton, comprising N,N-DimethylN&#39;&#39;-(2-methyl-4-chlorophenyl)-formamidine (Chlorphenamidine) and a compound selected among the group comprising 2(Diethoxyphosphinylimino)-4-methyl-1,3-dithiolane (Cytrolane) and 2-(Diethoxyphosphinothioylimino)-1,3-dithiolane (Cyolane) or a mixture thereof, and a method for controlling insects with said composition.

llnited States Patent Hadomi [451 Dec. 24, 11974 INSECTICIDAL COMPOSITIONS AND METHODS OF KILLING INSECTS USING A MIXTURE OF CYTROLANE AND CHLORPHENAMIDINE Menashe Hadomi, Tel-Avht, Israel C.T.S. Chemicals & Technical Supplies Ltd., Tel-Aviv, Israel Filed: Sept. 15, 1971 Appl. No.: 180,881

Inventor:

Assignee:

Foreign Application Priority Data Sept. 24, 1970 Israel 35342 US. Cl. 424/202, 424/300 Int. Cl A01n 9/02, AOln 9/12, AOln 9/22 Field of Search 424/202, 330

References Cited UNITED STATES PATENTS 7/1965 Addor 260/327 M 3,378,437 4/l968 Arndt et al. 424/330 Primary Examiner-Albert T. Meyers Assistant ExaminerAllen J. Robinson Attorney, Agent, or Firm-Ostrolenk, Faber, Gerb & Soffen '(Cytrolane) and 2-(Diethoxyphosphinothioylimino)- l,3-dithiolane (Cyolane) or a mixture thereof, and a method for controlling insects with said composition.

5 Claims, No Drawings llNSlECTllCIDAL COMPOSITIONS AND METHODS OF KILLING INSECTS USING A MIXTURE OF CYTROLANE AND CHLORPHENAMIDINE The present invention relates to a composition for 5 controlling certain lepidepteran larvae, in particular those which harm to cotton, e.g. Spodoptera littoralis Boisd also called Prodenia litura, and Earias insulana also called spiny bollworm.

Prodenia, when in the larval stage, causes great harm to agricultural field crops, in particular to cotton.

So far no compound or composition has been found which satisfactorily controls the above pest. The control is either not sufficiently complete or the lasting effect is not long enough. Moreover, there is not known any compound or composition which is effective enough against both the eggs and the larvae.

N,N-Dimethyl-N-(2-methyl-4-chlorophenyl)- formamidine (hereinafter called Chlorphenamidine) is effective against eggs of certain insects, inter alia, of Prodenia. However, it has nearly no effect on the Prodenia larvae. Neither does it sufficiently control the spiny bollworm.

2-(Diethoxyphosphinylamino)-4-methyl-1,3- dithiolane (hereinafter called Cytrolane) is an insecticide. However, it is not effective at all against the eggs of Prodenia and not sufficiently effective against the larval stages.

2-(Diethoxyphosphinothioylimino)-1,3- dithiolane(hereinafter called Cyolane) is quite effective in killing the Prodenia larvae but has no effect on the eggs.

The most effective compound against the spiny bollworm is the dimethyl cis-1-methyI-Z-methylcarbonylvinyl phosphate (hereinafter called Nuvacron). However, Nuvacron has nearly no effect on the other above mentioned larvae which attack cotton plants.

It has now surprisingly been found that if Chlorphenamidine is admixed whith Cyolane and/or Cytrolane a composition is obtained which is very effective in controlling both eggs and the larvae of Prodenia. This effect is long lasting and thus the Prodenia can be controlled by the said composition nearly completely. Moreover, this composition is also effective against the other larvae mentioned above attacking cotton, i.e., the spiny bollworm, a result of which is that one composition can be used to protect the cotton from the attack of said larval pests.

As will be shown hereinafter the mutual influence of Chlorphenamidine and Cytrolane on each other is a synergistic one. The insecticidal activity of Cytrolane against the Prodenia larvae is increased and the ovicidal activity of Chlorphenamidine against the Prodenia eggs is increased as well.

The present invention thus consists in an insecticidal composition comprising Chlorphenamidine and a compound selected among the group comprising Cytrolane and Cyolane or a mixture thereof.

The ratio between Chlorphenamidine and Cytrolane and/or Cyolane may be varied to a great extent. The preferred range is about 1:2 up to about 1:10.

The composition according to the present invention is prepared by admixing the individual ingredients together. Said composition may comprise any further desired compound provided it is compatible with the two essential active compounds of the new composition and has no adverse effect on the activity thereof. Such additional compounds may be, e.g. solvents, emulsifiers, additional insecticides, carriers, etc. The commercial available Chlorphenamidine, Cytrolane and Cyolane mostly comprise such compounds.

The present invention consists also in a method for controlling insects, particularly those larvae which attack e.g. Prodenia and spiny bollworm in an infected area, which comprises applying the above new composition to said area.

The new composition is preferably applied by spraying a solution of the new composition in water onto said area.

The quantity of active compounds to be utilised varies in accordance with the grade of infestation of the area. Preferably approximately 50-200 g of the composition for 1000 m dissolved in various amounts of water is employed.

The invention will now be illustrated by the following examples without being limited by them.

EXAMPLE 1 The effectiveness of Cytrolane in comparison with that of a composition according to the present invention was tested against Prodenia larvae in the laboratory. The results are shown in Table I.

Table l Cytrolane Chlorphenamidine Kill after 24 Hours 3 'y 2.4y 0.6-y 98% The same test was made against Prodenia eggs. The results are shown in Table 11.

From the above results the mutual synergistic influence of Chlorphenamidine and Cytrolane on each other becomes clearly apparent.

EXAMPLE 2 6 Plots each of 200 m of a cotton plantation infected with Prodenia were treated as follows:

a. Plots 1 and 3 were control plots and thus not treated;

b. Plots 2 and 6 were treated with a composition of Chlorphenamidine and Cytrolane (ratio ccz880 cc) diluted in water. (60 cc composition in 4 l of water were sprayed on each plot).

c. Plot 4 was treated with 60 cc of Cyolane in 4 l of water; and

(1. Plot 5 was treated with 60 cc of a composition of Chlorphenamidine and Cyolane (ratio 120 ccz880 cc) dissolved in 4 l of water.

The first count was made after 6 days and the results are shown in Table 111.

Table 111 Plot larvae 3-10mm larvae 11-25mm larvae exceeding long long 25mm in length 1 46 14 l 2 1 0 3 l8 7 4 4 3 0 0 5 O 0 0 6 3 0 0 The count was made by counting 2 m of length four times in each plot.

Thereafter plot 1 was disregarded.

Plot 7 was added which was treated with 40 ml of a composition of Chlorphenamidine and Cytrolane (ratio 120 cc:880 cc) dissolved in 4 1 of water.

Moreover, a further control plot 8 was added.

A further count was made after another week and the results obtained are shown in Table IV.

Table IV Plot larvae 3-10mm larvae 11-25mm larvae exceeding long long 25mm in length Said results prove the good effectiveness of the new compositions according to the present invention.

EXAMPLE 3 Table V Plot Larva 3-l0mm Larva of 11-25mm Larva exceeding The count was performed as in Example 2.

EXAMPLE 4 The results of further experiments are illustrated in the following tables, the compounds utilised in said experiment were commercially available solutions, they were sprayed on the infested areas in that about 1 1 of said solution was dissolved in about 7 1 of water. The meaning of a.i. is active ingredient and of e.c. is emulsifiable concentrate.

Table V1 Field trial at Nir Galim to compare 009 with Cyolane and Cytrolane in the control of Spodoprera linoralis in cotton (variety 442) Product Rate used at Average number of Mean from 3 plots of the Mean from 3 plots of the 1st and 2nd S. lirwralis larvae averages of S. lilmralir averages of S. lilmmlis dates of spray foci found in 300 larvae in 4 X 4 m. segments larvae in 2 X 4 m.

treatment meter row segments of rows segments of rows liter/hectare Block 1: Spray treatments on 19.771 and 28.7.71

19.7.71 28.7.71 count: 15.7.71 count: 25.7.71 count: 1.8.71

l/ha l/ha small metotal small melarge total small melargc total dium dium dium 1. Cyolane 1.0 3.0 10.6 6.3 16.3 0.8 15.2 7.0 23.0 0.2 0 (1.2 0.4 2. Cytrolane 1.0 2.0 12.6 9.3 21.9 10.0 10.0 5.8 25.8 0.3 0.5 1.2 2.3 3. Cytrolane 1.5 3.0 8.0 9.3 17.3 1.3 3.8 5.3 10.4 0 0.2 0.2 0.4 4. 009 1.0 2.0 13.3 7.0 20.3 0.3 4.8 6.3 11.4 0 0.3 0.4 0.7 5.009 1.5 3.0 15.3 13.0 28.3 0 4.2 5.8 10.0 0 (1 0.2 0.2 6. untreated control 3 6 9 9.0 12.0 21.0 1.0 1.3 2.8 5.1 Block 11: Spray treatment on 27.7.71 only count: 25.7.71 count: 2.8.71

27.7.71 small melarge total small melarge total dium dium NM 1. Cyolane 3.0 2.0 15.2 13.2 30.4 0 0.8 0.1 0.9 2. Cytrolane 2.0 16.5 9.3 12.3 38.1 0 4.2 8.9 13.1 3. Cytrolane 3.0 5.3 5.8 12.2 23.3 0 1.4 1.7 3.1 4.009 2.0 6.0 7.0 18.0 31.0 0 0.2 0.3 0.5 5.009 3 O 2.2 12.2 16.6 31.0 0 0.1 0.5 0.6 6. untreated control 0 1.0 10.0 11.0 2.3 2.5 0.8 5.6

cotton sown on 24.5.71

Cyolane (American Cyanamid1 25; a.i. e.c. Cytrolane (American Cyanamid) 25% a.i. e.c. 009 20% a.i.Cytro1ane 107: a.i. chlnrnphenamidine Table V11 Field trial at Nir Galim to compare 009 with Cytrolane and Nuvacron in the control of Spodoplera lilloralis in cotton (variety 442) Rate used Mean from the replicates No. of Mean from the replicates No. of at indicated of the averages of S. repliof the averages of S. replidates littoralis larvae in cates littoralis larvae in catcs 2 X 4m. segments of rows 2 X 4m. segments of rows Block 11: spray treatments on 16.8.71 only spray: 16.8.71 count: 29.8.71

small melarge total dium 3.0 l/ha 1.2 8.7 6.0 15.9 3 Cytrolane 3.0 do. 7.5 39.3 14.3 51.1 3 Nuvacron 2.5 do. 2.0 36.5 37.5 76.0 1 Control (untreated) 0.5 3.5 11.0 15.0 1 Block 11: spray treatments on 11.8.71 and 16.8.71

spray: 11.8.71 16.8.71 count: 29.8.71

small melarge total dium 009 3.0 l/ha 3.0 l/ha 0.8 0.5 0.5 1.8 2 Cytrolane 3.0 do. 30 do. 1.3 4.7 0.3 6.3 3 Nuvacron 2.5 do. 2.5 do. 17.5 30.5 48.0 2 Control (untreated) 0.5 3.5 11.0 15.0 1 Block I: spray treatments on 13.8.71 and 23.8.71 spray: spray: 13.8.71 23.8.71 count: 27.8.71 count: 30.8.71

small melarge total small melarge total dium dium 009 2.0 or 3.0 3.0 l/ha 0 1.0 0.2 1.2 3 0 0.7 0.3 1.0 3 Cytrolane 2.0 or 3.0 3.0 do. 0 3.2 0 3.2 3 Nuvacron 2.5 /ha 2.5 do. 1.8 18.5 6.8 27.1 2 3.3 27.6 31.0 61.9 3 untreated control 0 1 1 0 9.5 20.5 1

Table V111 Field trial at Nir Galim to compare 009 with Cytrolane and Nuvacron in the control of Earia: insulana Boisd. in cotton (variety 442) Product Rate No. of count: count: Count:

2 days before treatment 3 days after treatment 7 days after treatment l/ha replicates infested bolls healthy total infested bolls healtotal infested bolls healthy total with without bolls No. of with without Thy No. of with with bolls No. of larvae larvae bolls lar larvae bolls bolls larvae out bolls counted vae examined larvae examined 71 4.8 7.6 87.6 9.9 9.4 80.7 8.8 14.8 76.4 Cytrolane 2.0 3 no. 16 44 340 400 31 43 177 251 87 70 292 449 72 4.0 11.0 85.0 12.4 17.1 70.5 19.4 15.6 65.0 Cytrolane 3.0 3 no. 32 35 333 400 29 53 143 225 83 74 273 430 8.0 8.7 83.3 12.9 23.6 63.5 19.3 17.2 63.5 Nuvacron 2.5 3 no. 22 53 425 500 28 45 198 271 28 41 381 450 72 4.4 10.6 85.0 10.3 15.7 73.0 6.2 9.1 84.7 untreated 1 no. 13 26 161 200 11 10 32 47 38 67 152 control 7c 6.5 13.0 80.5 20.8 18.7 60.5 30.9 25.0 44.1

Cyolane (American Cyanamidl 25 7: a.i. e.c. Cytrolane (American Cyanamid) 25 7t a.i. e.c. 009 20 Z a.i. Cytrolane 10% a.i. chlorophenamidine Table [X Field trial at Nir Galim to compare 009 with Cytrolane and Nuvacron in the control of Eariax insulana Boisd. in cotton (variety 442) Product Rate No. of count: count: count:

one day before treatment 3 days after treatment 8 days after treatment l/ha replicates infested bolls healthy total infested bolls healthy total infested bolls healthy total with with bolls number with withbolls number with withbolls number larvae out of bolls larvae out of bolls larvae out of bolls larvae counted larvae examined larvae examined 7: 13.6 14.8 71/6 15.7 14.7 69.7 6.3 21.7 72.0 Cytrol- 3.0 3 no. 48 46 271 368 41 87 192 320 21 67 212 300 ane 13.0 12.5 74.5 12.8 27.2 70.0 7.0 22.3 70.7 Nuvacron 2.5 4 no. 18 18 100 136 13 27 60 100 5 20 untreated 1 no. 18 33 72 123 18 9 20 12 38 50 100 control "/1 14.6 26.8 58.6 38.3 19.1 42.6 12.0 38.0 50.0

Cyolane 25% a.i. e.c. Cytrolane 2591 a.i. e.c. 009 20% a.i. Cytrolane +1071 a.i. chlorphenamidine WMMM m mmm m :8 @R E D m 2 h o com p wwm E m m E w 295852 com N mm o 2 o w 3m aw NH 0 m I. 383.520 com M N. fi o 2 m vmm Rm 2 o m c o o H 8m M 2m a m 0 3: can 5mm 0 2 m; W m wwN ww w J. I 252 c m @3583 32 2:22 352 m znfi ucwa ww 6 m 7 W fiz m i 55 5;, B E -Z m M B .8955 33B 2E2 @855 unoq mwb 2 Sta 92% .5 fiqwflsmw om un 94% o 5580 u E O Um mqmfim o 8 0 mm o m A 0 mm m cm ldcozwm l 2 a8 a a3? Q: A 3 mm m M H NE M n Wm 3 2 H 0 w p m Hm m 5 m H N. xw m n2 Sm N8 s w W m m m E w mm o? M mv M E m m N R w 2 u 8m W 5% 2 5 M m 39% o? Md. W2 W2 M m o m Edi 3 16 mwm m K g M New mh 58am m o N Q O u 1 g M 9% 2H 2 M w a 2% M 5 3 an B EW n o m 92 80 cnm 5 a 0% N m mm m Am n 2 u ymw m o 3m 8 g 8 5 5385 mace. @552 $5 mgwumnoh 5a 5530 55 215 $22 $52 $3 32 an: 555x05 6 m 215 M 53? 5%, 55 M 2: 2 83 .6 R G a s 3 fifi m E3? Er; 3 32:52 3mm Bag Sa a .5955: E38 E32 E i; 388 2:5 838E QH QP .Stw nu 3 SEME Q um 33w gnu m 580 E2335 2 33a E 5560 cotton which comprises applying an effective insecticidal amount of the composition of claim 1 to an infected area.

4. The method of claim 3 wherein said composition is applied as a solution in water.

5. The method of claim 3 wherein 50 to 200 grams of said composition in 17 to 25 liters of water is used per 1,000 cubic meters of infected area.

* l l l 

1. A SYNERGISTIC INSECTICIDAL COMPOSITION COMPRISING N,NDIMETHYL-N''-(2-METHYL-4-CHLOROPHENYL0-FORMAMIDINE AND 2-(DIETHOXYPHOSPHINYLIMINO)-4-METHYL-1,3-DITHIOLANE IN A RATIO OF 1:2 TO 1:10, RESPECTIVELY.
 2. The synergistic insecticidal composition of claim 1 wherein the ratio is 1:2.
 3. A method for controlling insect larvae harmful to cotton which comprises applying an effective insecticidal amount of the composition of claim 1 to an infected area.
 4. The method of claim 3 wherein said composition is applied as a solution in water.
 5. The method of claim 3 wherein 50 to 200 grams of said composition in 17 to 25 liters of water is used per 1,000 cubic meters of infected area. 